There has been a significant interest in lithium superoxide (LiO2), due to recent research into lithium-oxygen batteries, and the possibility that lithium superoxide may be an intermediate in the formation of lithium peroxide in lithium air cells. The first step in the oxygen reduction reaction (ORR) in a lithium air cell has been speculated to be the reduction of O2 to O2−, through a one-electron transfer, which is followed by the reaction with a lithium cation to form LiO2 (Eqs. 1 and 2):O2+e−→O2−  (Eq. 1)O2−+Li+→LiO2  (Eq. 2)Lithium peroxide (Li2O2) can be then formed by the reaction of LiO2 with Li+ through a second electron transfer, as shown in Eq. 3:LiO2+e−+Li+→Li2O2  (Eq. 3)Alternatively, Li2O2 may be generated via the disproportionation reaction of LiO2:2LiO2→Li2O2+O2  (Eq. 4)